JP2010518242A - Peroxide activated oxometalate based formulation for removing etching residues - Google Patents
Peroxide activated oxometalate based formulation for removing etching residues Download PDFInfo
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- JP2010518242A JP2010518242A JP2009549586A JP2009549586A JP2010518242A JP 2010518242 A JP2010518242 A JP 2010518242A JP 2009549586 A JP2009549586 A JP 2009549586A JP 2009549586 A JP2009549586 A JP 2009549586A JP 2010518242 A JP2010518242 A JP 2010518242A
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- Prior art keywords
- formulation
- metal
- peroxide
- cleaning composition
- acid
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 238000009472 formulation Methods 0.000 title claims abstract description 66
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 title description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 238000004140 cleaning Methods 0.000 claims abstract description 43
- 238000004377 microelectronic Methods 0.000 claims abstract description 24
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 230000007797 corrosion Effects 0.000 claims abstract description 20
- 239000000356 contaminant Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013011 aqueous formulation Substances 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 239000013020 final formulation Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 13
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- -1 ion silicate Chemical class 0.000 claims description 11
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- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
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- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical group C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 claims description 5
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- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 4
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical group OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 3
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 241001168730 Simo Species 0.000 claims description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims 2
- 229920002120 photoresistant polymer Polymers 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 235000012431 wafers Nutrition 0.000 description 12
- 239000002585 base Substances 0.000 description 9
- 238000004380 ashing Methods 0.000 description 8
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- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 229910052802 copper Inorganic materials 0.000 description 1
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- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
- KFJNCGCKGILQMF-UHFFFAOYSA-M dibutyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(C)CCCC KFJNCGCKGILQMF-UHFFFAOYSA-M 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- IIAPBJPXNIYANW-UHFFFAOYSA-M ethyl-(2-hydroxyethyl)-dimethylazanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CCO IIAPBJPXNIYANW-UHFFFAOYSA-M 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- KTDMLSMSWDJKGA-UHFFFAOYSA-M methyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(CCC)CCC KTDMLSMSWDJKGA-UHFFFAOYSA-M 0.000 description 1
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- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
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- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- HPWUYZIJILJHNG-UHFFFAOYSA-M tributyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](CCO)(CCCC)CCCC HPWUYZIJILJHNG-UHFFFAOYSA-M 0.000 description 1
- FYFNFZLMMGXBMT-UHFFFAOYSA-M tributyl(ethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](CC)(CCCC)CCCC FYFNFZLMMGXBMT-UHFFFAOYSA-M 0.000 description 1
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Dental Preparations (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
（ａ）水と、（ｂ）アルカリ性ｐＨの最終調合物を産生するのに十分な量の、少なくとも１つの無金属イオン塩基と、（ｃ）少なくとも１つの水溶性無金属イオンケイ酸塩腐食防止剤約０．０１〜約５重量％（％ＳｉＯ２として表される）と、（ｄ）少なくとも１つの金属キレート剤約０．０１〜約１０重量％と、（ｅ）少なくとも１つのオキシメタレート０超〜約２．０重量％とを含む、高アルカリ性水性調合物が本発明によって提供される。このような調合物は過酸化物と化合されて、ペルオキシメタラートが形成され、マイクロ電子洗浄組成物が産生される。マイクロ電子デバイス、たとえばマイクロ電子基材から汚染物質および残留物を除去するために使用される。(A) water, (b) at least one metal-free ionic base in an amount sufficient to produce an alkaline pH final formulation, and (c) at least one water-soluble metal-free ionic corrosion inhibitor. From about 0.01 to about 5% by weight (expressed as% SiO 2 ); (d) from about 0.01 to about 10% by weight of at least one metal chelator; and (e) at least one oxymetallate 0 Highly alkaline aqueous formulations comprising greater than about 2.0% by weight are provided by the present invention. Such formulations are combined with peroxides to form peroxymetalates and produce microelectronic cleaning compositions. Used to remove contaminants and residues from microelectronic devices such as microelectronic substrates.
Description
［０００１］本発明は、マイクロ電子デバイスからエッチング残留物を除去するのに有用な組成物であって、良好な耐食性と洗浄効率の改善を提供する組成物に関するものである。詳細には、本発明は、マイクロ電子産業で特に有用であり、金属線およびビアを有するマイクロ電子基材からエッチング残留物を除去するのに特に有効である、過酸化物によって活性化された水性高アルカリ性オキソメタレート調合物を提供する。本発明は、このような組成物を利用してこのようなマイクロ電子基材およびデバイスを洗浄する方法も提供する。 [0001] The present invention relates to a composition useful for removing etch residues from microelectronic devices, which provides good corrosion resistance and improved cleaning efficiency. In particular, the present invention is particularly useful in the microelectronic industry and is a peroxide-activated aqueous solution that is particularly effective in removing etching residues from microelectronic substrates having metal lines and vias. A highly alkaline oxometalate formulation is provided. The present invention also provides methods for cleaning such microelectronic substrates and devices utilizing such compositions.
［０００２］マイクロ電子製造の重要な部分は、画像をマスクまたはレチクルから所望の回路層に転写するためにフォトレジストを使用することである。所望の画像転写が達成された後に、エッチング工程を使用して所望の構造を形成する。このようにして形成される最も一般的な構造は、金属線およびビアである。金属線を使用して、同じ製造層に存在する集積回路の各種の部品間に電気接続部を形成する。ビアは、誘電体層を通じてエッチングされ、その後、導電性金属で充填されるホールである。これらのビアを使用して、集積回路の各種の垂直層間に電気接続部を作製する。金属線やビアの形成に使用する工程では、一般にハロゲン含有ガスが使用される。 [0002] An important part of microelectronic manufacturing is the use of photoresist to transfer an image from a mask or reticle to a desired circuit layer. After the desired image transfer is achieved, an etching process is used to form the desired structure. The most common structures formed in this way are metal lines and vias. Metal wires are used to form electrical connections between various components of the integrated circuit that are present in the same manufacturing layer. A via is a hole that is etched through a dielectric layer and then filled with a conductive metal. These vias are used to make electrical connections between the various vertical layers of the integrated circuit. In a process used for forming a metal wire or via, a halogen-containing gas is generally used.
［０００３］エッチング工程が完了した後に、化学剥離溶液によって、または酸素プラズマ灰化工程によってフォトレジストを除去できる。問題は、このようなエッチング工程が通常の化学剥離溶液によって除去できない高度に不溶性の金属含有残留物を産生することである。また、特にアルミニウムベースの集積回路の場合には、灰化工程の間に金属含有残留物は酸化され、除去するのがなお困難になる。非特許文献１を参照されたい。 [0003] After the etching process is completed, the photoresist can be removed by a chemical stripping solution or by an oxygen plasma ashing process. The problem is that such an etching process produces highly insoluble metal-containing residues that cannot be removed by conventional chemical stripping solutions. Also, particularly in the case of aluminum-based integrated circuits, metal-containing residues are oxidized during the ashing process and are still difficult to remove. See Non-Patent Document 1.
［０００４］このようなエッチング工程の例は、集積回路上での金属線のパターン形成である。この工程では、金属フィルム上にフォトレジストコーティングが塗布されて、次にマスクまたはレチクルを通じて撮像され、フォトレジストコーティング中のパターンが選択的に露光される。コーティングは現像されて、使用したフォトレジストのトーンに応じて露光または未露光フォトレジストのどちらかが除去されて、金属パターン上にフォトレジストが生成される。残存したフォトレジストは通例、高温にて高硬度焼付けされて、溶媒を除去し、場合によりポリマーマトリクスを架橋させる。実際の金属エッチングステップが次に実施される。このエッチングステップにより、フォトレジストに被覆されていない金属が気体プラズマの作用によって除去される。このような金属の除去によって、パターンがフォトレジスト層から金属層に転写される。残存するフォトレジストは次に有機剥離溶液によって、または酸素プラズマ灰化処置によって除去（「剥離」）される。灰化処置の後に、液体有機剥離溶液を使用するすすぎステップが続くことが多い。しかし現在利用できる剥離溶液、通常はアルカリ性剥離溶液は、集積回路に不溶性金属酸化物や他の金属含有残留物を残存させる。 [0004] An example of such an etching process is patterning of metal lines on an integrated circuit. In this step, a photoresist coating is applied on the metal film and then imaged through a mask or reticle to selectively expose the pattern in the photoresist coating. The coating is developed to remove either exposed or unexposed photoresist, depending on the tone of photoresist used, to produce a photoresist on the metal pattern. The remaining photoresist is typically baked with high hardness at high temperatures to remove the solvent and optionally crosslink the polymer matrix. The actual metal etching step is then performed. By this etching step, the metal not coated with the photoresist is removed by the action of the gas plasma. By such metal removal, the pattern is transferred from the photoresist layer to the metal layer. The remaining photoresist is then removed ("stripped") by an organic stripping solution or by an oxygen plasma ashing procedure. The ashing treatment is often followed by a rinsing step using a liquid organic stripping solution. However, currently available stripping solutions, usually alkaline stripping solutions, leave insoluble metal oxides and other metal-containing residues in the integrated circuit.
［０００５］このようなエッチング工程の別の例は、集積回路上でのビア（相互接続ホール）のパターン形成である。この工程では、誘電体フィルム上にフォトレジストコーティングが塗布されて、次にマスクまたはレチクルを通じて撮像され、フォトレジストコーティング中のパターンが選択的に露光される。コーティングは現像されて、使用したフォトレジストのトーンに応じて露光または未露光フォトレジストのどちらかが除去されて、金属パターン上にフォトレジストが生成される。残存したフォトレジストは通常、高温にて高硬度焼付けされて、溶媒が除去され、場合によりポリマーマトリクスが架橋される。実際の誘電体エッチングステップが次に実施される。このエッチングステップにより、フォトレジストに被覆されていない誘電体が気体プラズマの作用によって除去される。このような誘電体の除去によって、パターンがフォトレジスト層から誘電体層に転写される。残存するフォトレジストは次に有機剥離溶液によって、または酸素プラズマ灰化処置によって除去（「剥離」）される。通例、誘電体は、下にある金属層が露出される箇所までエッチングされる。金属／誘電体境界には通例、チタンまたは窒化チタン反射防止または拡散バリア層が存在する。この境界層は、通常、貫通してエッチングされて、下にある金属を露出させる。含有されるチタンまたは窒化チタン層を貫通するエッチングの作用により、ビアの内側に形成されるエッチング残留物にチタンが取り込まれることが見出された。酸素プラズマ灰化は、これらのビア残留物を酸化して、除去するのをより困難にする。したがって、このような残留物の洗浄を可能にするために、剥離溶液にチタン残留物除去促進剤を添加する必要がある。非特許文献２を参照されたい。灰化処置の後に、液体有機剥離溶液を使用するすすぎステップが続くことが多い。しかし現在利用できる剥離溶液、通常はアルカリ性剥離溶液は、集積回路に不溶性金属酸化物や他の金属含有残留物を残存させる。有機溶媒含有率が高いヒドロキシルアミンベースの剥離剤や灰化後残留物除去剤はいくつか市場に出回っているが、ビアや金属線に見られる他の残留物に対するほど有効ではない。その剥離剤や除去剤は、ビアや金属線から残留物を除去するために高温（通例は６５℃以上）も必要とする。 [0005] Another example of such an etching process is the patterning of vias (interconnect holes) on an integrated circuit. In this step, a photoresist coating is applied on the dielectric film and then imaged through a mask or reticle to selectively expose the pattern in the photoresist coating. The coating is developed to remove either exposed or unexposed photoresist, depending on the tone of photoresist used, to produce a photoresist on the metal pattern. The remaining photoresist is usually baked with high hardness at high temperature to remove the solvent and optionally crosslink the polymer matrix. The actual dielectric etch step is then performed. By this etching step, the dielectric not covered with the photoresist is removed by the action of the gas plasma. Such removal of the dielectric transfers the pattern from the photoresist layer to the dielectric layer. The remaining photoresist is then removed ("stripped") by an organic stripping solution or by an oxygen plasma ashing procedure. Typically, the dielectric is etched to the point where the underlying metal layer is exposed. There is typically a titanium or titanium nitride antireflection or diffusion barrier layer at the metal / dielectric interface. This boundary layer is usually etched through to expose the underlying metal. It has been found that the action of etching through the contained titanium or titanium nitride layer incorporates titanium into the etching residue formed inside the via. Oxygen plasma ashing oxidizes these via residues and makes them more difficult to remove. Therefore, in order to enable such residue cleaning, it is necessary to add a titanium residue removal accelerator to the stripping solution. See Non-Patent Document 2. The ashing treatment is often followed by a rinsing step using a liquid organic stripping solution. However, currently available stripping solutions, usually alkaline stripping solutions, leave insoluble metal oxides and other metal-containing residues in the integrated circuit. Several hydroxylamine-based strippers and post-ash residue removers with high organic solvent content are on the market but are not as effective as other residues found in vias and metal lines. The stripper and remover also require high temperatures (typically 65 ° C. or higher) to remove residues from vias and metal wires.
［０００６］金属フィルムを含有する超小型回路へアルカリ性剥離剤を使用すると、特に、アルミニウムあるいはアルミニウムまたはチタンなどの活性金属と、銅またはタングステンなどのより陽性の金属との各種の組み合せまたは合金を含有する金属フィルムと共に使用したときに、必ずしも良質の回路が産生されるわけではなかった。多種多様の金属腐食、たとえば腐食ウィスカー、電解腐食、点食、金属線のノッチングが、少なくとも一部は、金属とアルカリ性剥離剤との反応のために観察されてきた。さらに非特許文献３によって、ウエハーから有機剥離剤を除去するのに必要である水洗ステップまでごくわずかな腐食作用が起こっていることが示されている。腐食は明らかに、金属に、すすぎステップの間に存在する強アルカリ性水溶液を接触させた結果である。アルミニウム金属は、このような条件下で急速に腐食することが公知である（非特許文献４）。 [0006] The use of alkaline release agents in microcircuits containing metal films, in particular, contains various combinations or alloys of active metals such as aluminum or aluminum or titanium and more positive metals such as copper or tungsten. When used with a metal film, good quality circuits were not always produced. A wide variety of metal corrosion, such as corrosion whiskers, electrolytic corrosion, pitting, metal wire notching, has been observed, at least in part, due to the reaction of the metal with the alkaline stripper. Furthermore, Non-Patent Document 3 shows that only a slight corrosive action occurs until the water washing step necessary to remove the organic release agent from the wafer. Corrosion is clearly the result of contacting the metal with a strong alkaline aqueous solution present during the rinsing step. Aluminum metal is known to corrode rapidly under such conditions (Non-Patent Document 4).
［０００７］この腐食問題を回避するために使用された以前の方法は、イソプロピルアルコールなどの非アルカリ性有機溶媒を用いた中間すすぎを利用した。しかしこのような方法は費用がかかり、望ましくない安全上、衛生化学上、そして環境上の影響を有する。 [0007] Previous methods used to avoid this corrosion problem have utilized intermediate rinses with non-alkaline organic solvents such as isopropyl alcohol. However, such methods are expensive and have undesirable safety, hygiene and environmental impacts.
［０００８］特許文献１では、フォトレジスト残留物や他の望ましくない汚染物質を除去することによって、半導体ウエハー基材を剥離または洗浄するための、マイクロ電子産業で有用な水性アルカリ性組成物が開示されている。水性組成物は通例、（ａ）約１０〜１３のｐＨを生じるのに十分な量の、１つ以上の無金属イオン塩基と、（ｂ）水溶性の無金属イオンケイ酸塩約０．０１〜約５重量％（％ＳｉＯ２として表される）と、（ｃ）１つ以上の金属キレート剤約０．０１〜約１０重量％と、（ｄ）場合により、他の成分とを含有する。 [0008] Patent Document 1 discloses an aqueous alkaline composition useful in the microelectronic industry for stripping or cleaning semiconductor wafer substrates by removing photoresist residues and other undesirable contaminants. ing. The aqueous composition typically has (a) an amount of one or more metal-free ion bases sufficient to produce a pH of about 10-13, and (b) a water-soluble metal-free ion silicate of about 0.01- About 5 wt% (expressed as% SiO 2 ), (c) about 0.01 to about 10 wt% of one or more metal chelators, and (d) optionally other ingredients.
［０００９］しかし従来技術で開示された組成物のいずれも、代表的なエッチング工程後に残存するすべての有機汚染物質や金属含有残留物を効果的に除去しない。ケイ素含有残留物は、これらの調合物を使用して除去するのが特に困難である。したがって、集積回路を損傷することなく無機および有機汚染物質をこのような基材から除去することによって、半導体ウエハー基材を洗浄する剥離組成物への要求がある。単体ウエハーツールが幅広く使用されているので、金属および有機汚染物質を従来技術の組成物よりも短時間かつ低温で除去することができる調合物への要求もある。このような組成物は、集積回路を部分的に構成する金属構成要素を腐食してはならず、中間すすぎによって発生する費用や悪影響を回避すべきである。タングステンおよびアルミニウム線は、段落［０００８］で議論した調合物による洗浄時に特に腐食を受けやすい。 [0009] However, none of the compositions disclosed in the prior art effectively removes all organic contaminants and metal-containing residues remaining after a typical etching process. Silicon-containing residues are particularly difficult to remove using these formulations. Accordingly, there is a need for a stripping composition that cleans semiconductor wafer substrates by removing inorganic and organic contaminants from such substrates without damaging the integrated circuit. Because of the widespread use of single wafer tools, there is also a need for formulations that can remove metal and organic contaminants in a shorter time and at lower temperatures than prior art compositions. Such a composition should not corrode the metal components that partially comprise the integrated circuit and should avoid the costs and adverse effects caused by intermediate rinsing. Tungsten and aluminum wires are particularly susceptible to corrosion when washed with the formulations discussed in paragraph [0008].
［００１０］本発明により、（ａ）水と、（ｂ）アルカリ性ｐＨ、好ましくは約１１〜約１３．４のアルカリ性ｐＨの最終組成物を産生するのに十分な量の、少なくとも１つの、無金属イオン塩基と、（ｃ）少なくとも１つの水溶性の無金属イオンケイ酸塩腐食防止剤約０．０１〜約５重量％（％ＳｉＯ２として表される）と、（ｄ）少なくとも１つの金属キレート剤約０．０１〜約１０重量％と、（ｅ）少なくとも１つのオキソメタレート０超〜約２．０重量％とを含む、高アルカリ性水性調合物が提供される。このような調合物は、オキソメタレートと反応する少なくとも１つの過酸化物と化合してペルオキソメタレートを形成して、水性アルカリ性マイクロ電子洗浄組成物を生じる。水の量は、調合物または組成物の１００重量％の残りである。本出願で示すパーセンテージはすべて、別途指摘しない限り重量パーセントであり、組成物の全重量に基づいている。 [0010] In accordance with the present invention, (a) water and (b) at least one, none, in an amount sufficient to produce a final composition having an alkaline pH, preferably from about 11 to about 13.4. A metal ion base; (c) at least one water-soluble metal-free ion silicate corrosion inhibitor from about 0.01 to about 5% by weight (expressed as% SiO 2 ); and (d) at least one metal chelate. A highly alkaline aqueous formulation is provided comprising about 0.01 to about 10% by weight of the agent and (e) at least one oxometalate greater than 0 to about 2.0% by weight. Such formulations combine with at least one peroxide that reacts with the oxometalate to form a peroxometalate, resulting in an aqueous alkaline microelectronic cleaning composition. The amount of water is the balance of 100% by weight of the formulation or composition. All percentages indicated in this application are weight percentages unless otherwise indicated and are based on the total weight of the composition.
［００１１］洗浄組成物を半導体ウエハー基材と、基材表面から望ましくない汚染物質および／または残留物を洗浄するのに十分な時間にわたって、十分な温度にて接触させる。本発明の組成物は、耐食性の向上と洗浄効率の改善を提供する。 [0011] The cleaning composition is contacted with the semiconductor wafer substrate at a sufficient temperature for a time sufficient to clean unwanted contaminants and / or residues from the substrate surface. The composition of the present invention provides improved corrosion resistance and improved cleaning efficiency.
［００１２］（ａ）水と、（ｂ）アルカリ性ｐＨ、好ましくは約１１〜約１３．４のアルカリ性ｐＨの最終調合物を産生するのに十分な量の、少なくとも１つの無金属イオン塩基と、（ｃ）少なくとも１つの水溶性の無金属イオンケイ酸塩腐食防止剤約０．０１〜約５重量％（％ＳｉＯ２として表される）と、（ｄ）少なくとも１つの金属キレート剤約０．０１〜約１０重量％と、（ｅ）少なくとも１つのオキソメタレート０〜約２．０重量％とを含む、本発明の高アルカリ性水性調合物が本発明によって提供される。このような調合物を、調合物のオキソメタレートと反応性である少なくとも１つの過酸化物と化合させて、得られた洗浄組成物の使用前にペルオキソメタレートが形成されるようにする。得られた組成物を半導体ウエハー基材などのマイクロ電子デバイスと、基材表面から望ましくない汚染物質および／または残留物を洗浄するのに十分な時間にわたって十分な温度にて接触させる。 [0012] (a) water and (b) at least one metal-free ionic base in an amount sufficient to produce a final formulation at an alkaline pH, preferably from about 11 to about 13.4. (C) at least one water-soluble metal-free ion silicate corrosion inhibitor from about 0.01 to about 5% by weight (expressed as% SiO 2 ); and (d) at least one metal chelator about 0.01. High alkaline aqueous formulations of the present invention are provided by the present invention comprising from about 10% by weight and (e) at least one oxometallate from 0 to about 2.0% by weight. Such a formulation is combined with at least one peroxide that is reactive with the oxometallate of the formulation so that the peroxometalate is formed prior to use of the resulting cleaning composition. The resulting composition is contacted with a microelectronic device, such as a semiconductor wafer substrate, at a sufficient temperature for a time sufficient to clean unwanted contaminants and / or residues from the substrate surface.
［００１３］本発明は、半導体ウエハー表面から汚染物質および残留物を剥離および洗浄するために過酸化物と化合する新たな水性調合物を提供し、該調合物は水（好ましくは高純度脱イオン水）と、１つ以上の無金属イオン塩基と、１つ以上の無金属イオンケイ酸塩腐食防止剤と、１つ以上の金属キレート剤と、１つ以上のオキソメタレートとを含有する。 [0013] The present invention provides a new aqueous formulation that combines with peroxide to strip and clean contaminants and residues from a semiconductor wafer surface, the formulation being water (preferably high purity deionized). Water), one or more metal-free ionic bases, one or more metal-free ionic corrosion inhibitors, one or more metal chelators, and one or more oxometallates.
［００１４］いずれの適切な塩基も、本発明の水性調合物で使用できる。塩基は、好ましくは第４級アンモニウムヒドロキシド、たとえばテトラアルキルアンモニウムヒドロキシド（一般にアルキルまたはアルコキシ基中に炭素原子１〜４個のヒドロキシ−およびアルコキシ−含有アルキル基を含む）である。これらのアルカリ性物質のうち最も好ましいのは、テトラメチルアンモニウムヒドロキシドおよびトリメチル−２−ヒドロキシエチルアンモニウムヒドロキシド（コリン）である。他の有用な第４級アンモニウムヒドロキシドとしては：トリメチル−３−ヒドロキシプロピルアンモニウムヒドロキシド、トリメチル−３−ヒドロキシブチルアンモニウムヒドロキシド、トリメチル−４−ヒドロキシブチルアンモニウムヒドロキシド、トリエチル−２−ヒドロキシエチルアンモニウムヒドロキシド、トリプロピル−２−ヒドロキシエチルアンモニウムヒドロキシド、トリブチル−２−ヒドロキシエチルアンモニウムヒドロキシド、ジメチルエチル−２−ヒドロキシエチルアンモニウムヒドロキシド、ジメチルジ（２−ヒドロキシエチル）アンモニウムヒドロキシド、モノメチルトリ（２−ヒドロキシエチル）アンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、モノメチル−トリエチルアンモニウムヒドロキシド、モノメチルトリプロピルアンモニウムヒドロキシド、モノメチルトリブチルアンモニウムヒドロキシド、モノエチルトリメチルアンモニウムヒドロキシド、モノエチルトリブチルアンモニウムヒドロキシド、ジメチルジエチルアンモニウムヒドロキシド、ジメチルジブチルアンモニウムヒドロキシドなど、およびその混合物が挙げられる。 [0014] Any suitable base can be used in the aqueous formulations of the present invention. The base is preferably a quaternary ammonium hydroxide, such as a tetraalkylammonium hydroxide (generally comprising hydroxy- and alkoxy-containing alkyl groups of 1 to 4 carbon atoms in the alkyl or alkoxy group). Most preferred among these alkaline substances are tetramethylammonium hydroxide and trimethyl-2-hydroxyethylammonium hydroxide (choline). Other useful quaternary ammonium hydroxides are: trimethyl-3-hydroxypropylammonium hydroxide, trimethyl-3-hydroxybutylammonium hydroxide, trimethyl-4-hydroxybutylammonium hydroxide, triethyl-2-hydroxyethylammonium Hydroxide, tripropyl-2-hydroxyethylammonium hydroxide, tributyl-2-hydroxyethylammonium hydroxide, dimethylethyl-2-hydroxyethylammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, monomethyltri (2 -Hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Trabutylammonium hydroxide, monomethyl-triethylammonium hydroxide, monomethyltripropylammonium hydroxide, monomethyltributylammonium hydroxide, monoethyltrimethylammonium hydroxide, monoethyltributylammonium hydroxide, dimethyldiethylammonium hydroxide, dimethyldibutylammonium hydroxide And mixtures thereof.
［００１５］本発明で機能する他の塩基としては、アンモニウムヒドロキシド、有機アミン、特にアルカノールアミン、たとえば２−アミノエタノール、１−アミノ−２−プロパノール、１−アミノ−３−プロパノール、２−（２−アミノエトキシ）エタノール、２−（２−アミノエチルアミノ）エタノール、２−（２−アミノエチルアミノ）エチルアミンなど、および他の有機強塩基、たとえばグアニジン、１，３−ペンタンジアミン、４−アミノメチル−１，８−オクタンジアミン、アミノエチルピペラジン、４−（３−アミノプロピル）モルホリン、１，２−ジアミノシクロヘキサン、トリス（２−アミノエチル）アミン、２−メチル−１，５−ペンタンジアミンおよびヒドロキシルアミンが挙げられる。ナトリウムまたはカリウムなどの金属イオンを含有するアルカリ性溶液も作用しうるが、発生することが考えられる残留金属汚染物質のために好ましくない。これらのさらなるアルカリ性成分の混合物、特にアンモニウムヒドロキシドと上述のテトラアルキルアンモニウムヒドロキシドとの混合物も有用である。 [0015] Other bases that function in the present invention include ammonium hydroxide, organic amines, especially alkanolamines such as 2-aminoethanol, 1-amino-2-propanol, 1-amino-3-propanol, 2- ( 2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) ethylamine, and other organic strong bases such as guanidine, 1,3-pentanediamine, 4-amino Methyl-1,8-octanediamine, aminoethylpiperazine, 4- (3-aminopropyl) morpholine, 1,2-diaminocyclohexane, tris (2-aminoethyl) amine, 2-methyl-1,5-pentanediamine and Hydroxylamine is mentioned. Alkaline solutions containing metal ions such as sodium or potassium can also work, but are not preferred due to residual metal contaminants that may be generated. Mixtures of these further alkaline components are also useful, particularly mixtures of ammonium hydroxide and the tetraalkylammonium hydroxide described above.
［００１６］無金属イオン塩基は調合物で利用されて、最終調合物に高いアルカリ性、一般に約１１〜約１３．４のｐＨを与える。 [0016] Metal-free ionic bases are utilized in the formulations to give the final formulation a high alkalinity, generally a pH of about 11 to about 13.4.
［００１７］いずれの適切な無金属イオンケイ酸塩も本発明の調合物で使用できる。ケイ酸塩は、好ましくは第４級アンモニウムシリケート、たとえばテトラアルキルアンモニウムシリケート（一般にアルキルまたはアルコキシ基中に炭素原子１〜４個のヒドロキシ−およびアルコキシ−含有アルキル基を含む）である。最も好ましい無金属イオンケイ酸塩成分は、テトラメチルアンモニウムシリケートである。本発明の他の適切な無金属イオンケイ酸塩源は、高アルカリ性洗浄剤に以下の物質のいずれか１つ以上を溶解させることによってインサイチューで産生できる。洗浄剤でケイ酸塩を産生させる適切な無金属イオン物質は、固体シリコンウエハー、ケイ酸、コロイド状シリカ、ヒュームドシリカあるいはシリコンまたはシリカの他のいずれかの適切な形である。 [0017] Any suitable metal-free ion silicate can be used in the formulations of the present invention. The silicate is preferably a quaternary ammonium silicate, such as a tetraalkylammonium silicate (generally comprising hydroxy- and alkoxy-containing alkyl groups of 1 to 4 carbon atoms in the alkyl or alkoxy group). The most preferred metal-free ion silicate component is tetramethylammonium silicate. Other suitable metal-free ion silicate sources of the present invention can be produced in situ by dissolving any one or more of the following materials in a highly alkaline detergent. Suitable metal-free ionic materials for producing silicates with detergents are solid silicon wafers, silicic acid, colloidal silica, fumed silica or any other suitable form of silicon or silica.
［００１８］少なくとも１つの無金属イオンケイ酸塩が調合物中に約０．０１〜約５重量％、好ましくは約０．０１〜約２％の量で存在するであろう。 [0018] At least one metal-free ionic silicate will be present in the formulation in an amount of about 0.01 to about 5% by weight, preferably about 0.01 to about 2%.
［００１９］本発明の調合物は適切な１つ以上の金属キレート剤を用いても調合され、調合物が溶液中に金属を保持して、ウエハー基材上の金属残留物の溶解を促進する能力を向上させる。この目的に有用な金属キレート剤の代表的な例としては、以下の有機酸ならびにその異性体および塩：（エチレンジニトリロ）四酢酸（ＥＤＴＡ）、ブチレンジアミン四酢酸、シクロヘキサン−１，２−ジアミン四酢酸（ＣｙＤＴＡ）、ジエチレントリアミン五酢酸（ＤＥＴＰＡ）、エチレンジアミンテトラプロピオン酸、（ヒドロキシエチル）エチレンジアミン三酢酸（ＨＥＤＴＡ）、Ｎ，Ｎ，Ｎ’，Ｎ’−エチレンジアミンテトラ（メチレンホスホン）酸（ＥＤＴＭＰ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）、１，３−ジアミノ−２−ヒドロキシプロパン−Ｎ，Ｎ，Ｎ’，Ｎ’−四酢酸（ＤＨＰＴＡ）、メチルイミノ二酢酸、プロピレンジアミン四酢酸、ニトロロ三酢酸（ＮＴＡ）、クエン酸、酒石酸、グルコン酸、糖酸、グリセリン酸、シュウ酸、フタル酸、マレイン酸、マンデル酸、マロン酸、乳酸、サリチル酸、カテコール、没食子酸、没食子酸プロピル、ピロガロール、８−ヒドロキシキノリン、およびシステインである。
［００２０］金属キレート剤として好ましいのは、アミノカルボン酸、たとえばシクロヘキサン−１，２−ジアミン四酢酸（ＣｙＤＴＡ）である。このクラスの金属キレート剤は、プラズマ「灰化」後に金属線およびビアに対して通例見出されるアルミニウム含有残基に対して高い親和性を有する。加えて、このクラスの金属キレート剤のｐＫａとしては、通例、本発明の組成物の性能を改善する約１２のｐＫａが挙げられる。
[0019] Formulations of the present invention are also formulated with one or more suitable metal chelators, the formulation holding the metal in solution and promoting dissolution of metal residues on the wafer substrate. Improve ability. Representative examples of metal chelators useful for this purpose include the following organic acids and isomers and salts thereof: (ethylenedinitrilo) tetraacetic acid (EDTA), butylenediaminetetraacetic acid, cyclohexane-1,2-diamine Tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N, N, N ′, N′-ethylenediaminetetra (methylenephosphonic) acid (EDTMP), Triethylenetetramine hexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrotriacetic acid (NTA) ), Citric acid, tartaric acid, gluconic acid, sugar acid, glycerin Acids, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, catechol, gallic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine.
[0020] Preferred as the metal chelator is an aminocarboxylic acid, such as cyclohexane-1,2-diaminetetraacetic acid (CyDTA). This class of metal chelators has a high affinity for aluminum-containing residues commonly found for metal lines and vias after plasma “ashing”. In addition, the pKa of this class of metal chelators typically includes about 12 pKa that improves the performance of the compositions of the invention.
［００２１］少なくとも１つの金属キレート剤が調合物中に約０．０１〜約１０重量％の量で、好ましくは約０．０１〜約２％の量で存在する。 [0021] At least one metal chelator is present in the formulation in an amount of about 0.01 to about 10% by weight, preferably in an amount of about 0.01 to about 2%.
［００２２］周期律表の第Ｖ族および第ＶＩ族からの遷移金属のいずれの適切なオキソメタレートも、本発明の調合物で利用できる。オキソメタレート成分は、単核オキソメタレート、ホモ多核オキソメタレート、およびヘテロ多核オキソメタレートより選択される１つ以上のオキソメタレートを含むことができる。本発明の遷移金属オキソメタレートは、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）、ニオブ（Ｎｂ）、クロム（Ｃｒ）またはタンタル（Ｔａ）のオキソメタレートを含む。オキサメタレートは、調合物中に０超〜約２重量％の量で、好ましくは約０．０１〜２重量％の量で存在するであろう。 [0022] Any suitable oxometalates of transition metals from Groups V and VI of the Periodic Table can be utilized in the formulations of the present invention. The oxometalate component can include one or more oxometalates selected from mononuclear oxometalates, homopolynuclear oxometalates, and heteropolynuclear oxometalates. The transition metal oxometalates of the present invention include oxometalates of molybdenum (Mo), tungsten (W), vanadium (V), niobium (Nb), chromium (Cr) or tantalum (Ta). The oxametalate will be present in the formulation in an amount greater than 0 to about 2% by weight, preferably in an amount of about 0.01-2% by weight.
［００２３］適切な単核オキソメタレートとしては、式［ＭＯｐ］ｎ−Ｚ＋のオキソメタレートが挙げられ、式中、Ｍは、Ｃｒ、Ｖ、Ｍｏ、Ｗ、Ｎｂ、およびＴａなどの高酸化状態早期遷移金属であり、Ｚは電荷を平衡させる対イオンである。最も好ましい電荷を平衡させる対イオンは、プロトン、テトラアルキルアンモニウム、およびアンモニウムカチオンである。ナトリウムまたはカリウムなどの金属イオンも作用しうるが、発生することが考えられる残留金属汚染物質のために好ましくない。このような適切な単核オキソメタレートの一例はたとえば（ＮＨ４）２ＭｏＯ４であり、式中、ＮＨ４ ＋は電荷を平衡させる対イオンであり、ＭｏＯ４ −はオキソメタレートである。 [0023] Suitable mononuclear oxometalates include oxometalates of the formula [MOp] n- Z + , where M is a high such as Cr, V, Mo, W, Nb, and Ta. An oxidation state early transition metal, Z is a counter ion that balances the charge. The most preferred counter ions that balance the charge are protons, tetraalkylammonium, and ammonium cations. Metal ions such as sodium or potassium can also act, but are not preferred due to residual metal contaminants that may be generated. An example of such a suitable mononuclear oxometalate is, for example, (NH 4 ) 2 MoO 4 , where NH 4 + is a counter ion that balances the charge and MoO 4 − is an oxometalate.
［００２４］適切なホモ多核オキソメタレートとしては、式［ＭｍＯｐ］ｎ−Ｚ＋のオキソメタレートが挙げられ、式中、Ｍは、Ｃｒ、Ｖ、Ｍｏ、Ｗ、Ｎｂ、およびＴａなどの高酸化状態早期遷移金属であり、Ｚは電荷を平衡させる対イオンである。これらは単核オキソメタレートから酸との縮合によって形成される。このような適切なホモ多核オキソメタレートの一例はたとえば（ＮＨ４）６Ｍｏ７Ｏ２４であり、式中、ＮＨ４ ＋は電荷を平衡させる対イオンであり、Ｍｏ７Ｏ２４ ６−はホモ多核オキソメタレートである。適切なヘテロ多核オキソメタレートとしては、式［ＸｘＭｍＯｐ］ｎ−Ｚ＋のオキソメタレートが挙げられ、式中、Ｍは、Ｃｒ、Ｖ、Ｍｏ、Ｗ、Ｎｂ、およびＴａなどの高酸化状態早期遷移金属であり；Ｘは、遷移金属または主族元素のどちらかでありうるヘテロ原子であり、Ｚは電荷を平衡させる対イオンである。ヘテロ多核オキソメタレートの一例は、Ｈ４ＳｉＷ１２Ｏ４０であり、式中、Ｈ＋は電荷を平衡させる対イオンであり、Ｓｉはヘテロ原子Ｘであり、Ｗは早期遷移金属Ｍである。 [0024] Suitable homo- polynuclear oxometallate formula [M m O p] n- Z + oxometallates are mentioned in, in the formula, M, Cr, V, Mo, W, Nb, and Ta Z is a counter ion that balances the charge. They are formed from mononuclear oxometalates by condensation with acids. An example of such a suitable homopolynuclear oxometalate is, for example, (NH 4 ) 6 Mo 7 O 24 , where NH 4 + is a counter ion that balances the charge, and Mo 7 O 24 6− is a homoion. It is a polynuclear oxometalate. Suitable hetero polynuclear oxometallate formula [X x M m O p] n- Z + of oxometallates are mentioned, in the formula, M, Cr, V, Mo, W, Nb, and Ta, etc. X is a heteroatom that can be either a transition metal or a main group element, and Z is a counter ion that balances the charge. An example of a heteropolynuclear oxometalate is H 4 SiW 12 O 40 , where H + is a counter ion that balances the charge, Si is a heteroatom X, and W is an early transition metal M.
［００２５］本発明の調合物は、洗浄組成物の有効性にとって有害でない任意の成分、たとえば界面活性剤、残留物除去促進剤などを含有することができる。 [0025] The formulations of the present invention can contain optional ingredients that are not detrimental to the effectiveness of the cleaning composition, such as surfactants, residue removal accelerators, and the like.
［００２６］本発明の調合物に適切なオキソメタレートとしては、これに限定されるわけではないが、モリブデン酸アンモニウム（（ＮＨ４）２ＭｏＯ４）、タングステン酸アンモニウム（（ＮＨ４）２ＷＯ４）、タングステン酸（Ｈ２ＷＯ４）、メタバナジン酸アンモニウム（ＮＨ４ＶＯ３）、ヘプタモリブデン酸アンモニウム（（ＮＨ４）６Ｍｏ７Ｏ２４）、メタタングステン酸アンモニウム（（ＮＨ４）６Ｈ２Ｗ１２Ｏ４０）、パラタングステン酸アンモニウム（（ＮＨ４）１０Ｈ２Ｗ１２Ｏ４２）、デカバナジウム酸テトラメチルアンモニウム（（ＴＭＡ）４Ｈ２Ｖ１０Ｏ２８）、デカニオブ酸テトラメチルアンモニウム（（ＴＭＡ）６Ｎｂ１０Ｏ２８）、二クロム酸アンモニウム（（ＮＨ４）２Ｃｒ２Ｏ７）、ホスホモリブデン酸アンモニウム（（ＮＨ４）３ＰＭｏ１２Ｏ４０、シリコタングステン酸（Ｈ４ＳｉＷ１２Ｏ４０）、ホスホタングステン酸（Ｈ３ＰＷ１２Ｏ４０）、ホスホモリブデン酸（Ｈ３ＰＭｏ１２Ｏ４０）、シリコモリブデン酸（Ｈ４ＳｉＭｏ１２Ｏ４０）、リン酸モリブドバナド（Ｈ５ＰＭｏ１０Ｖ２Ｏ４０）が挙げられる。 [0026] Suitable oxometalates for the formulations of the present invention include, but are not limited to, ammonium molybdate ((NH 4 ) 2 MoO 4 ), ammonium tungstate ((NH 4 ) 2 WO 4 ), tungstic acid (H 2 WO 4 ), ammonium metavanadate (NH 4 VO 3 ), ammonium heptamolybdate ((NH 4 ) 6 Mo 7 O 24 ), ammonium metatungstate ((NH 4 ) 6 H 2 W 12 O 40 ), ammonium paratungstate ((NH 4 ) 10 H 2 W 12 O 42 ), tetramethylammonium decabanadate ((TMA) 4 H 2 V 10 O 28 ), tetramethylammonium decanioate (( TMA) 6 Nb 10 O 28) , ammonium dichromate (( H 4) 2 Cr 2 O 7 ), phosphonium ammonium molybdate ((NH 4) 3 PMo 12 O 40, silicotungstic acid (H 4 SiW 12 O 40) , phosphotungstic acid (H 3 PW 12 O 40) , phospho molybdate (H 3 PMo 12 O 40) , silicomolybdic acid (H 4 SiMo 12 O 40) , and the like Moribudobanado phosphate (H 5 PMo 10 V 2 O 40) is.
［００２７］本発明の好ましい調合物の例としては、これに限定されるわけではないが、テトラメチルアンモニウムヒドロキシド２．１％、テトラメチルアンモニウムシリケート０．１４％、トランス−１，２−シクロヘキサンジアミン四酢酸０．１２％、および約モリブデン酸アンモニウムまたはシリコタングステン酸０．０１〜約２％および１００％までの残量の水を含む調合物が挙げられる。 [0027] Examples of preferred formulations of the present invention include, but are not limited to, tetramethylammonium hydroxide 2.1%, tetramethylammonium silicate 0.14%, trans-1,2-cyclohexane Formulations containing 0.12% diaminetetraacetic acid and from about 0.01 to about 2% and up to 100% residual water of about ammonium molybdate or silicotungstic acid.
［００２８］上述の調合物は、少なくとも１つの過酸化物と約５：１〜約４０：１の前記調合物の過酸化物に対する比で、好ましくは１５：１〜３０：１の比で、最も好ましくは２０：１の比で化合されて、マイクロ電子洗浄組成物を提供するであろう。上述の調合物のオキソメタレートと反応性であり、ペルオキソメタレートを形成するいずれの過酸化物も利用できる。適切な過酸化物としては、過酸化水素；ペルオキシ酸、たとえばペルオキシ二リン酸（Ｈ４Ｐ２Ｏ８）、ペルオキシ二硫酸（Ｈ４Ｓ２Ｏ８）、フタルイミドペルオキシカプロン酸、ペルオキシ酢酸（Ｃ２Ｈ４Ｏ３）、ペルオキシ安息香酸、ジペルオキシフタル酸、およびその塩；および過酸化アルキル、たとえば過酸化ベンゾイル、過酸化メチルエチルケトン、過酸化ジクミル、過酸化ｔｅｒｔ−ブチルクミルが挙げられる。好ましい過酸化物は、過酸化水素である。 [0028] The above formulation is in a ratio of at least one peroxide to a peroxide of about 5: 1 to about 40: 1, preferably in a ratio of 15: 1 to 30: 1. Most preferably, it will be combined in a 20: 1 ratio to provide a microelectronic cleaning composition. Any peroxide that is reactive with the oxometalates of the above-described formulations and forms peroxometalates can be utilized. Suitable peroxides include hydrogen peroxide; peroxy acids such as peroxydiphosphoric acid (H 4 P 2 O 8 ), peroxydisulfuric acid (H 4 S 2 O 8 ), phthalimido peroxycaproic acid, peroxyacetic acid (C 2 H 4 O 3), peroxybenzoic acid, diperoxyphthalic acid, and salts thereof; and alkyl peroxides, such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and peroxide tert- cumyl. A preferred peroxide is hydrogen peroxide.
［００２９］洗浄効率の向上は、これらのオキソメタレート種による過酸化物の活性化の結果であると考えられる。塩基性溶液中で、オキソメタレート（金属＝ＷＶＩ、ＭｏＶＩ、ＣｒＶＩ、ＶＶ、ＮｂＶ、およびＴａＶ）は過酸化物と反応して、無機ペルオキソメタレートを形成する。これらのペルオキソメタレートは洗浄を２つの方法で向上させる。第１に、ペルオキソメタレートは分解して一重項酸素、すなわち過酸化水素よりも強いオキシダントである高い反応性ラジカル酸化剤を産生する。この一重項酸素は残留物の酸化を改善して、したがって残留物の溶解を改善できると考えられる。ペルオキシメタレートは、過酸化物による有機物の酸化にとって効率的な触媒であることも公知である。この触媒活性は、炭素ベース残留物の酸化および除去を促進することができる。 [0029] The improvement in cleaning efficiency is believed to be the result of peroxide activation by these oxometalate species. In basic solution, oxometalates (metal = W VI , Mo VI , Cr VI , V V , Nb V , and Ta V ) react with peroxides to form inorganic peroxometalates. These peroxometalates improve cleaning in two ways. First, peroxometalates decompose to produce singlet oxygen, a highly reactive radical oxidant that is a stronger oxidant than hydrogen peroxide. This singlet oxygen is thought to improve the oxidation of the residue and thus improve the dissolution of the residue. Peroxymetalates are also known to be efficient catalysts for the oxidation of organics with peroxides. This catalytic activity can facilitate the oxidation and removal of carbon-based residues.
［００３０］化合溶液中で産生した、得られたペルオキソメタレートの分解のために、これらの溶液の寿命は一般に制限されている。ペルオキソモリブデートによって生成された溶液の赤色に基づいて、モリブデン酸アンモニウムを含有する、段落［００２７］の好ましい調合物は、過酸化水素（２０％）と２０：１希釈で混合されたときに、２５℃にて５分（２％モリブデン酸アンモニウム）〜４５分（０．０１％モリブデン酸アンモニウム）の寿命を示す。シリコタングステン酸を含有する、段落［００２７］の好ましい調合物の場合、２０％過酸化水素と混合されている（２０：１）調合物から生じる洗浄組成物の寿命ははるかに長く、色変化に基づいて４５分（２％シリコタングステン酸）〜５時間（０．０１％シリコタングステン酸）である。２０：１希釈で過酸化水素２０％と混合されたときのシリコタングステン酸（０．５％）を含有する、段落［００２７］の好ましい調合物を含む洗浄組成物でのＡｌエッチング速度変化の測定値は、過酸化水素２０％と２０：１希釈で混合したときに、わずか３．５時間の浴寿命を示したが、組成物は過酸化水素を用いてスパイクすることによって活性化することができた。これらの組成物の加熱は、これらの組成物の寿命を劇的に短縮させる。 [0030] The lifetime of these solutions is generally limited due to degradation of the resulting peroxometalates produced in the combined solution. Based on the red color of the solution produced by peroxomolybdate, the preferred formulation of paragraph [0027], containing ammonium molybdate, when mixed with hydrogen peroxide (20%) at a 20: 1 dilution, It shows a lifetime of 5 minutes (2% ammonium molybdate) to 45 minutes (0.01% ammonium molybdate) at 25 ° C. In the case of the preferred formulation of paragraph [0027] containing silicotungstic acid, the cleaning composition resulting from the formulation mixed with 20% hydrogen peroxide (20: 1) has a much longer lifetime and color change. Based on 45 minutes (2% silicotungstic acid) to 5 hours (0.01% silicotungstic acid). Measurement of Al etch rate change in cleaning compositions containing the preferred formulation of paragraph [0027] containing silicotungstic acid (0.5%) when mixed with 20% hydrogen peroxide at a 20: 1 dilution. The values showed a bath life of only 3.5 hours when mixed with 20% hydrogen peroxide at a 20: 1 dilution, but the composition can be activated by spiking with hydrogen peroxide. did it. Heating these compositions dramatically shortens the life of these compositions.
［００３１］半導体およびマイクロチップ産業でこれらの組成物にオキソメタレートを使用することの他の１つの懸念事項は、処理後にウエハー表面に金属が残存する可能性である。モリブデンおよびタングステンのこれらの組成物からの金属吸収は、ＸＰＳ（Ｘ線光電子分光法）を使用して試験した。過酸化水素（２０％）と２０：１の比で混合された、モリブデン酸アンモニウムおよびシリコタングステートを含有する段落［００２７］の好ましい調合物中でのＡｌおよびＴＥＯＳの処理、脱イオン水中での１分間のすすぎ、アルゴン中での乾燥の後、ウエハー表面のいずれにもＭｏまたはＷは観察されなかった。このことは、これらの金属アニオンをウエハー表面から容易にすすぐことが可能であり、遷移金属汚染物質がこれらの調合物による問題であるはずがないことを示唆している。 [0031] Another concern of using oxometalates in these compositions in the semiconductor and microchip industries is the potential for metal to remain on the wafer surface after processing. Metal absorption from these compositions of molybdenum and tungsten was tested using XPS (X-ray photoelectron spectroscopy). Treatment of Al and TEOS in a preferred formulation of paragraph [0027] containing ammonium molybdate and silicotungstate mixed in a 20: 1 ratio with hydrogen peroxide (20%), in deionized water After rinsing for 1 minute and drying in argon, no Mo or W was observed on any of the wafer surfaces. This suggests that these metal anions can be easily rinsed from the wafer surface and that transition metal contaminants should not be a problem with these formulations.
［００３２］本発明の洗浄組成物のエッチング速度は、２０％過酸化水素を２０：１の希釈比で添加した段落［００２７］の好ましい調合物を用いて２５℃にて測定した。比較のために、オキソメタレートを用いずに対照調合物を調製した（対照調合物＝水、テトラメチルアンモニウムヒドロキシド２．１％、テトラメチルアンモニウムシリケート０．１４％、トランス−１，２−シクロヘキサンジアミン四酢酸０．１２％。シリコタングステン酸またはモリブデン酸アンモニウムを含有する試験を行ったすべての好ましい洗浄組成物が、対照調合物と比較してＡｌ、Ｔｉ、およびＴＥＯＳエッチング速度を著しく低下させたわけではないが、Ｗエッチング速度は対照調合物によって得たエッチング速度の約半分であった。 [0032] The etching rate of the cleaning composition of the present invention was measured at 25 ° C. using the preferred formulation of paragraph [0027] to which 20% hydrogen peroxide was added at a dilution ratio of 20: 1. For comparison, a control formulation was prepared without oxometallate (control formulation = water, tetramethylammonium hydroxide 2.1%, tetramethylammonium silicate 0.14%, trans-1,2- Cyclohexanediaminetetraacetic acid 0.12% All preferred cleaning compositions tested containing silicotungstic acid or ammonium molybdate significantly reduced Al, Ti, and TEOS etch rates compared to the control formulation. Although not, the W etch rate was about half that obtained with the control formulation.
［００３３］２０％過酸化水素を２０：１の比で添加したこれらの好ましい調合物の洗浄効率を、Ａｌ金属線およびビアの両方に対して試験した。対照として段落［００３２］の対照調合物を使用した。試験したＡｌ金属線の場合、対照調合物は４５℃にて５分後にすべての残留物を除去することだけはできたが、電解腐食は、２５℃にて５分後にも常に観察された。両方の好ましい調合物では、対照調合物と比較して電解腐食の劇的な減少が観察され、残留物除去は、より低温かつより短い処理時間で達成された。モリブデン酸アンモニウム（０．１％）を含有する好ましい調合物では、これらの金属線は２５℃にてわずか２分で、腐食を伴わずに洗浄された。シリコタングステン酸（０．５％）を含有する好ましい調合物では、金属線は２５℃にて２分で完全に洗浄され、腐食はほとんど観察されなかった。試験したＡｌビアの場合、２０％過酸化水素を２０：１の比で含む対照調合物は、ビアを２５℃にてわずか５分で洗浄することができた。シリコタングステン酸を含む好ましい調合物では、対照調合物で観察された腐食の増加を伴わずに、調合物の２０％過酸化水素に対するより高い比（３０：１）を使用できる。この場合、洗浄は２５℃にてわずか２分で行うことができる。 [0033] The cleaning efficiency of these preferred formulations with 20% hydrogen peroxide added in a 20: 1 ratio was tested against both Al metal lines and vias. The control formulation of paragraph [0032] was used as a control. For the Al metal wires tested, the control formulation was only able to remove all residues after 5 minutes at 45 ° C, but galvanic corrosion was always observed after 5 minutes at 25 ° C. In both preferred formulations, a dramatic reduction in galvanic corrosion was observed compared to the control formulation, and residue removal was achieved at lower temperatures and shorter processing times. In the preferred formulation containing ammonium molybdate (0.1%), these metal wires were cleaned without corrosion in only 2 minutes at 25 ° C. In the preferred formulation containing silicotungstic acid (0.5%), the metal wire was thoroughly cleaned in 2 minutes at 25 ° C. and little corrosion was observed. For the Al vias tested, a control formulation containing 20% hydrogen peroxide in a 20: 1 ratio was able to clean the vias at 25 ° C. in just 5 minutes. In a preferred formulation containing silicotungstic acid, a higher ratio of formulation to 20% hydrogen peroxide (30: 1) can be used without the increase in corrosion observed with the control formulation. In this case, washing can be performed at 25 ° C. in as little as 2 minutes.
［００３４］一般に、シリコタングステン酸およびモリブデン酸アルミニウムを含有する好ましい調合物は、対照調合物よりも腐食防止および洗浄効率が改善されたことを示す。また両方の場合で、タングステンエッチング速度は、対照調合物と比較してほぼ半分に短縮される。 [0034] In general, preferred formulations containing silicotungstic acid and aluminum molybdate show improved corrosion protection and cleaning efficiency over the control formulation. Also in both cases, the tungsten etch rate is reduced by almost half compared to the control formulation.
［００３５］本発明はその具体的な実施形態を参照して本明細書で説明されてきたが、本明細書に開示された本発明の概念の精神および範囲から逸脱することなく、変更、修飾および変形が行えることが認識される。したがって、添付した特許請求の範囲の精神および範囲に含まれるこのような変更、修飾および変形すべてが含まれることを意図する。 [0035] While this invention has been described herein with reference to specific embodiments thereof, alterations, modifications, and alterations can be made without departing from the spirit and scope of the inventive concepts disclosed herein. It will be appreciated that deformations can be made. Accordingly, it is intended to embrace all such alterations, modifications and variations that fall within the spirit and scope of the appended claims.
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- 2008-01-28 DE DE602008002819T patent/DE602008002819D1/en active Active
- 2008-01-28 PL PL08724882T patent/PL2111445T3/en unknown
- 2008-01-28 CN CN2008800051913A patent/CN101611130B/en active Active
- 2008-01-28 ES ES08724882T patent/ES2356109T3/en active Active
- 2008-01-28 KR KR1020097016902A patent/KR101446368B1/en active IP Right Grant
- 2008-01-28 BR BRPI0808074-7A patent/BRPI0808074A2/en not_active IP Right Cessation
- 2008-01-28 EP EP08724882A patent/EP2111445B1/en not_active Not-in-force
- 2008-01-28 JP JP2009549586A patent/JP2010518242A/en active Pending
- 2008-01-28 CA CA002677964A patent/CA2677964A1/en not_active Abandoned
- 2008-01-28 US US12/522,716 patent/US8183195B2/en not_active Expired - Fee Related
- 2008-01-28 AT AT08724882T patent/ATE483012T1/en active
- 2008-01-28 WO PCT/US2008/001103 patent/WO2008100377A1/en active Application Filing
- 2008-01-28 DK DK08724882.9T patent/DK2111445T3/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014104358A1 (en) * | 2012-12-28 | 2014-07-03 | 東ソー株式会社 | Group 5 metal oxo-alkoxo complex, method for producing same, and method for manufacturing group 5 metal oxide film |
| JP2014141473A (en) * | 2012-12-28 | 2014-08-07 | Tosoh Corp | Group 5 metal oxo-alkoxo complex, method of producing the same, and method of forming group 5 metal oxide film |
| US9663541B2 (en) | 2012-12-28 | 2017-05-30 | Tosoh Corporation | Group 5 metal oxo-alkoxo complex, method for producing same, and method for manufacturing group 5 metal oxide film |
| JP2015124159A (en) * | 2013-12-25 | 2015-07-06 | 東ソー株式会社 | Tantalum oxo-alkoxo complex, method of producing the same, and method of making tantalum oxide film |
| JP2015124158A (en) * | 2013-12-25 | 2015-07-06 | 東ソー株式会社 | Niobium oxo-alkoxo complex, method of producing the same, and method of making niobium oxide film |
| JP2016213337A (en) * | 2015-05-11 | 2016-12-15 | 株式会社エー・シー・イー | Method for wet etching of silicon wafer |
Also Published As
| Publication number | Publication date |
|---|---|
| IL199999A0 (en) | 2010-04-15 |
| WO2008100377A1 (en) | 2008-08-21 |
| ATE483012T1 (en) | 2010-10-15 |
| BRPI0808074A2 (en) | 2014-08-05 |
| ZA200905362B (en) | 2010-05-26 |
| KR101446368B1 (en) | 2014-10-01 |
| TW200907049A (en) | 2009-02-16 |
| KR20090110906A (en) | 2009-10-23 |
| EP2111445A1 (en) | 2009-10-28 |
| PL2111445T3 (en) | 2011-04-29 |
| DE602008002819D1 (en) | 2010-11-11 |
| IL199999A (en) | 2013-03-24 |
| PT2111445E (en) | 2010-12-29 |
| ES2356109T8 (en) | 2011-10-11 |
| ES2356109T3 (en) | 2011-04-05 |
| EP2111445B1 (en) | 2010-09-29 |
| US20100035786A1 (en) | 2010-02-11 |
| CN101611130A (en) | 2009-12-23 |
| DK2111445T3 (en) | 2011-01-17 |
| MY145938A (en) | 2012-05-31 |
| US8183195B2 (en) | 2012-05-22 |
| CN101611130B (en) | 2011-05-18 |
| CA2677964A1 (en) | 2008-08-21 |
| TWI441920B (en) | 2014-06-21 |
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